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111.
High‐performance liquid chromatography separation of unsaturated organic compounds by a monolithic silica column embedded with silver nanoparticles
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Yang Zhu Kei Morisato George Hasegawa Nirmalya Moitra Tsutomu Kiyomura Hiroki Kurata Kazuyoshi Kanamori Kazuki Nakanishi 《Journal of separation science》2015,38(16):2841-2847
The optimization of a porous structure to ensure good separation performances is always a significant issue in high‐performance liquid chromatography column design. Recently we reported the homogeneous embedment of Ag nanoparticles in periodic mesoporous silica monolith and the application of such Ag nanoparticles embedded silica monolith for the high‐performance liquid chromatography separation of polyaromatic hydrocarbons. However, the separation performance remains to be improved and the retention mechanism as compared with the Ag ion high‐performance liquid chromatography technique still needs to be clarified. In this research, Ag nanoparticles were introduced into a macro/mesoporous silica monolith with optimized pore parameters for high‐performance liquid chromatography separations. Baseline separation of benzene, naphthalene, anthracene, and pyrene was achieved with the theoretical plate number for analyte naphthalene as 36 000 m?1. Its separation function was further extended to cis/trans isomers of aromatic compounds where cis/trans stilbenes were chosen as a benchmark. Good separation of cis/trans‐stilbene with separation factor as 7 and theoretical plate number as 76 000 m?1 for cis‐stilbene was obtained. The trans isomer, however, is retained more strongly, which contradicts the long‐ established retention rule of Ag ion chromatography. Such behavior of Ag nanoparticles embedded in a silica column can be attributed to the differences in the molecular geometric configuration of cis/trans stilbenes. 相似文献
112.
A high-spin ground state is possible if a molecule has degenerate or pseudo-degenerate frontier orbitals. Since strong vibronic couplings, or electron-vibration interactions give rise to reduce the degeneracy or pseudo degeneracy, a lower-spin state is the ground state in such a molecule. Therefore small vibronic couplings are desirable for designing molecules with a high-spin ground state. Vibronic coupling constants of derivatives of m-phenylene diamine are evaluated. The calculated results are analyzed based on vibronic coupling density which enables us to control the vibronic coupling constants. Based on the vibronic coupling density analysis, we succeed in recovering the high-spin ground state from the closed-shell singlet ground state of a methoxy derivative of m-phenylene diamine by introducing an appropriate substituent. 相似文献
113.
When a mixture of o-alkynylaryl isocyanides and organic dichalcogenides such as diselenides or ditellurides was irradiated with light of wavelength over 300 or 400 nm, the intramolecular cyclization of the isocyanides took place to afford the corresponding 2,4-bischalcogenated quinolines selectively. The photochemical cyclization of 2-(phenylethynyl)phenyl isocyanide could also proceed in the presence of hydrogen transfer reagents such as tris(trimethylsilyl)silane, tributylgermyl hydride, alkanethiols, and benzeneselenol, providing the corresponding 3-phenylquinoline as the result of 2,4-dihydrogenation. 相似文献
114.
Iwata M Yazaki R Chen IH Sureshkumar D Kumagai N Shibasaki M 《Journal of the American Chemical Society》2011,133(14):5554-5560
A direct catalytic asymmetric aldol reaction of thioamides using a soft Lewis acid/hard Br?nsted base cooperative catalyst comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]PF(6)/LiOAr is described. Exclusive enolate generation from thioacetamides through a soft-soft interaction with the soft Lewis acid allowed for a direct aldol reaction to α-nonbranched aliphatic aldehydes, which are usually susceptible to self-condensation under conventional basic conditions. A hard Lewis basic phosphine oxide has emerged as an effective additive to constitute a highly active ternary soft Lewis acid/hard Br?nsted base/hard Lewis base cooperative catalyst, enabling a direct enantio- and diastereoselective aldol reaction of thiopropionamides. Strict control of the amount of the hard Lewis base was essential to drive the catalytic cycle efficiently with a minimized retro-aldol pathway, affording syn-aldol products with high stereoselectivity. Divergent transformation of the thioamide functionality is an obvious merit of the present aldol methodology, allowing for a facile transformation of the aldol product into the corresponding aldehyde, ketone, amide, amine, and ketoester. An aldehyde derived from the direct aldol reaction was subjected to a second direct aldol reaction, which proceeded in a catalyst-controlled manner to provide 1,3-diols with high stereoselectivity. 相似文献
115.
Maehara S Ikeda M Haraguchi H Kitamura C Nagoe T Ohashi K Shibuya H 《Chemical & pharmaceutical bulletin》2011,59(8):1042-1044
We investigated the microbial conversion of curcumin (1) using endophytic fungi associated with the rhizome of Curcuma longa (Zingiberaceae). We found that Diaporthe sp., an endophytic filamentous fungus, converts curcumin (1) into four colorless derivatives, namely (3R,5R)-tetrahydrocurcumin (2), a novel (3R,5S)-hexahydrocurcumin (3) named neohexahydrocurcumin, (3S,5S)-octahydrocurcumin (4) and meso-octahydrocurcumin (5). 相似文献
116.
Kim SY Kashiwada Y Kawazoe K Murakami K Sun HD Li SL Takaishi Y 《Chemical & pharmaceutical bulletin》2011,59(10):1281-1284
Four new lindenane sesquiterpenoid dimers, spicachlorantins G-J (1-4), were isolated from the roots of Chloranthus spicatus together with seven known compounds, including chloramultilide A, shizukaol B, shizukaol D, shizukaol F, shizukaol P, chlorahololide D, and cycloshizukaol A. The planar structures of the new compounds were established by 1D-, 2D-NMR, and MS analyses. The absolute configurations of these compounds were determined by analyzing rotating Overhauser enhancement and exchange spectroscopy (ROESY) and circular dichroism (CD) spectra. 相似文献
117.
Two new cannabinoid-like chromane and chromene derivatives named anthopogocyclolic acid (1) and anthopogochromenic acid (2) and five related compounds (3-7) which are known as synthetic analogues of cannabinoids: cannabichromene (CBC) type, cannabicyclol (CBL) type, and cannabicitran (CBT) type, have been isolated together with geranyl orsellinic acid (8) from the Chinese medicinal plant Rhododendron anthopogonoides. Their structures were elucidated based on spectroscopic and chemical evidence. The absolute configuration of the asymmetric carbons at C-2 of 1-7 was determined to be S from their circular dichroism (CD) spectra. Compounds 2, 4 and 6 inhibited compound 48/80-induced histamine release from rat peritoneal mast cells. 相似文献
118.
Enantioselective total synthesis of the biologically important indole alkaloids (+)-lysergol, (+)-isolysergol, and (+)-lysergic acid is described. Key features of these total synthesis include (1) a facile synthesis of a chiral 1,3-amino alcohol via the Pd(0)- and In(I)-mediated reductive coupling reaction between L-serine-derived 2-ethynylaziridine and formaldehyde; (2) the Cr(II)/Ni(0)-mediated Nozaki-Hiyama-Kishi (NHK) reaction of an indole-3-acetaldehyde with iodoalkyne; and (3) Pd(0)-catalyzed domino cyclization of an allene bearing amino and bromoindolyl groups. This domino cyclization enabled direct construction of the C/D ring system of the ergot alkaloids skeleton, as well as the creation of the C5 stereogenic center with transfer of the allenic axial chirality to the central chirality. 相似文献
119.
120.
Hideo Kojima Kazuyoshi Ozaki Noboru Matsumura Hiroo Inoue 《Journal of heterocyclic chemistry》1990,27(6):1845-1846
7-Substituted 2,3-bis(isopropylthio)naphth[1,8-bc]azepines 3a-c were synthesized in good yields by the reactions of 5-substituted 1-naphthylamines 2a-c with tris(isopropylthio)cyclopropenylium perchlorate ( 1 ) in acetonitrile under reflux. This reaction proceeds through the facile ring opening of 1 , followed by the intermediary formation of iminium salts 5a-c and then intramolecular cyclization. 相似文献